本文關(guān)鍵詞：環(huán)狀過氧化物對硫醚的氧化反應(yīng)研究　出處：《哈爾濱工業(yè)大學(xué)》2016年碩士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 鄰苯二甲酰過氧化物 溫和氧化劑 亞砜 氧化機(jī)理

【摘要】：亞砜化合物已經(jīng)廣泛用于生物醫(yī)藥和有機(jī)化學(xué)研究,引起了多個(gè)領(lǐng)域研究人員的重視。常見的亞砜類藥物有胃病良藥奧美拉唑,神經(jīng)性疾病藥物莫達(dá)非尼和心血管疾病類藥物磺吡酮等。同時(shí),在有機(jī)化學(xué)中手性亞砜類化合物還可作為手性助劑、手性配體和手性催化劑廣泛用于不對稱合成中。制備亞砜類化合物最直接的方法是將硫醚類化合物進(jìn)行氧化。近期,環(huán)狀二酰基過氧化物已成功用于烯烴的雙羥基化反應(yīng)和碳?xì)滏I的氧化反應(yīng),表現(xiàn)出溫和的氧化性能。本文以環(huán)狀二�；^氧化物為氧化劑,選擇性地將硫醚類化合物氧化為亞砜類化合物,并對反應(yīng)機(jī)理進(jìn)行探討。合成了兩種環(huán)狀二�；^氧化物,鄰苯二甲酰過氧化物(PPO)和環(huán)戊基丙二酰過氧化物(MPO)。以PPO為氧化劑對硫醚進(jìn)行氧化,高選擇性高收率地將硫醚類化合物氧化為亞砜,拓展了37個(gè)涵蓋多種官能團(tuán)的硫醚進(jìn)行普適性研究。以MPO為氧化劑,在溫和條件下高產(chǎn)率地合成了奧美拉唑。通過氣-質(zhì)檢測、核磁驗(yàn)證和DFT計(jì)算等,對環(huán)狀二酰基過氧化物的氧化機(jī)理進(jìn)行了探討,提出了可能的反應(yīng)機(jī)理。以環(huán)狀二�；^氧化物為氧化劑,將硫醚類化合物氧化為亞砜,操作簡單,無需使用其他催化劑和添加劑,氧化性能溫和,可選擇性地將硫醚氧化為亞砜,底物適應(yīng)性廣,具有良好的官能團(tuán)容忍度。
[Abstract]:Sulfoxide compounds have been widely used in biomedical and organic chemistry research, which has attracted the attention of researchers in many fields. Common sulfoxide drugs include omeprazole, a good medicine for stomach diseases. At the same time, chiral sulfoxide compounds can be used as chiral auxiliaries in organic chemistry. Chiral ligands and chiral catalysts are widely used in asymmetric synthesis. The most direct way to prepare sulfoxides is to oxidize sulfides. Cyclic diacylperoxides have been successfully used in the dihydroxylation of olefins and the oxidation of hydrocarbon bonds, showing mild oxidation properties. In this paper, cyclic diacyl peroxides are used as oxidants. Sulfides were selectively oxidized to sulfoxide compounds and the reaction mechanism was discussed. Two cyclic diacyl peroxides were synthesized. Phthalyl peroxide (PPO) and cyclopentyl malonyl peroxide (PPO) were used to oxidize sulfides to sulfoxide in high selectivity and yield. 37 sulfides covering a variety of functional groups were expanded to study their universality. Omeprazole was synthesized with high yield under mild conditions using MPO as oxidant. The oxidation mechanism of cyclic diacylperoxides was discussed and the possible reaction mechanism was proposed. The cyclic diacyl peroxide was used as oxidant. The thioether compounds are oxidized to sulfoxide, which is easy to operate and does not need other catalysts and additives. The oxidation performance is mild and the sulfoxide can be oxidized to sulfoxide selectively. The substrate has wide adaptability. Good tolerance of functional groups.
【學(xué)位授予單位】：哈爾濱工業(yè)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：O621.254.1

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